Synthetic rubber compositions



Modulus a+ 300.2 Elonqai'on, lbs. pzr' sq. Tensile Sheng-ih, lbs per' sq.n. L

Sept. 19, 1944.

Filed Feb. 13, 1943.

IZBO

Timz of Cui-z, min.

lnvenor; Th9dore W. Evans Patentedl Sept. 19,

srN'rnn'rro minnen comosrrroNs v TheodoreW. Evans, Oakland, Calif., assigner to Shell Development Company, San Francisco, Calif., a corporation of Delaware Application February is, 1943, serial No. 475,840

16 claims. This invention -relates to novel synthetic rub-A ber compositions. More particularly, -the invention pertains to compositions and their vulcanizates of polymers comprising 2-chlorol butadiene-1,3' softened with a member of a class 'of halogenated alkyl ethers.

Rubber-like polymers require the use of various mixed substances or particular chemical compounds to be .incorporated therewith for the purposeof softening the polymer to a workable state and to impart useful properties to compounded compositions and vulcanizates of such compositions. The particular softener employed in the composition has a marked influence on the properties of the final vulcanizates. It is desir- '15 able, in the synthetic rubber-like vulcanizates, that the softener beof such nature that 'the polymer vulcanizate will have proper extenslbili ity and resiliency 'while still retaining ahigh tensilestrength. ordinarily eiected in a heated pressure mould and the compounded polymers have poor ability to conduct heat, it is desirable, in manufacturing articles of considerable thickness from the com-- pounded polymers,- that' the properties of the vulcanizate' be not critical with respect to the time of cure, because the inner portions of large articles will besublected to the temperature of cure over shorter periods of 'time than outer portions, owing to slowness of heat conduction to the interior of the article. When the properties are critical (reaching a maximum or minimum) with respect to time of cure, large articles-have a marked variation of properties depending upon the distance from the surface of the article. Moreover, uniformness or fiatness of properties a with varying times of curel or vulcanization is to be desired so that inevitable variations in time which sometimes occur in commercial manufacturing practice will not yield articles of inferior -or useless properties. Among special properties which are to be desired in synthetic rubber compositions is` the ability of the vulcanizates to resist re. It is also desirable, when articles are manufactured from these compositions, that they do not tend to stiffen or become brittle when Subjected to low temperatures such as would be encountered inlrctic regions or at high-altitudes whichairplanes attain.-

It is an object of the present invention to provide vulcanizates of .polymers of 2-halobuta- Y diene-1,3, which have a dat cure, or substan- Further, since vincamzation is (Cl. 26o- 36) tially uniform physical properties even though the time of cure has been varied over considerable limits.

Another object is to provide synthetic rubber- 1,5' like compositions havingv therein a softener which greatlyvlncreases resistance of the vulcanizates to fire or burning.

A further object is to provide compositions of polymers of a 2-halo-butadiene-1,3 having ex- 10 cellent resistance to stiiening when subjected to low temperatures.

These and other objects of the invention will be apparent from the description of it given hereinafter. l

The compositions of the invention contain as a softener one or more compounds of a class of -halogenated alkyl ethers. 'I'hese halogenated alkyl ethers have identical or dierent groups attached to the ethereal oxygen atom which groups are halogen-substituted radicals containing 3 to 8 carbon atoms to each of which is linked at least two halogen atoms, but are devoid of'any halogen atoms on the alpha carbon atom thereof.

'I'he halogenated alkyl ethers contain the halo- Een atoms linked to carbon atoms in the carbon fchain of the alkyl group which are at least once removed from theethereal -oxygen atom, i. e. the compounds contain the halogen atoms linked to carbon atoms in the carbon chain of the alkyl 30 group, which chain has atleast one intervening carbon atom devoid of a halogen atom linked directly thereto between the ethereal oxygen atom and a carbon atom having ahalogen atom linked directly thereto. Such alpha-halogencontaining alkyl. ethers are too unstable and 4 easily hydrolyzable for use in the compositions. A preferred group oi softener compounds are those ethers wherein two halogen atoms are linked as substituents to each of the alkyl groupsl of the ether in the beta and gamma positions.

.The ethersof this type are described'and claimed in. copendingV application of Hearne and La `France, Serial No. 359,091 -led September 30, 1940. Representative members of the class of the halogenated alkyl ethers include such coni- A pounds as'tetrachlorov dipropyl ether, bis (d1- chloro isopropyl) ether, hexachloro dipropyl ether, octachloro dipropyl ether, pentachloro -dipropyl ether, tetrabromo dibutyl ether, tetra.-

chloro dipentyl ether, dichloro-bromo dipropyl ether,'-'tetrachloro dihexyl ether, tetrauoro diisobutyl ether, octachloro di-octyl ether, hexachloro di-tertiary butyl ether, as well as com` pounds represented by the following formulas:

emol-GHol-cHz-o-om-CHCx-CHCI 01GB, CHCI cH-o-CH l cmcl CHzF-CHF CH3-CH,-cHBr-CHBr-Cnro-CHrcHBr-CHBr-Cm-CH.

^ CH:Cl-CHCl-CHc1-CHro-Crh-CHCi-oncl-Cmcl cnafoHI-oHfo-cHf-oimfcinl 'I'he halogenated alkyl ethers employed as softeners in compositions of the invention, owing to the presence'therein of at least four halogen atoms, have the propertyvof imparting excellent ame resistance to the compositions, including the vulcanized compositions. As stated hereinbefore, it is necessary that the substituted alkyl groups linked to'the etheral oxygen atom of the softener compounds contain at least three, but not more than eight, carbon atoms, in each group. Compounds of similar type, but with only two carbon atoms in the alkyl groups are volatile and tend to.rather rapidly evaporate from the vulcanizates so as to render them with useless properties in a comparatively short time. The softener compounds used in the compositions of the invention also give excellent resistance against stiifening of ,chloroprene polymer vulcanizates at low temperatures. Similar' compounds which are halogenated aromatic ethers do not impart such low temperature properties to the vulcanizatesnor do halogenated waxes.

The synthetic elastomer constituents are rubber-like. materials such asv polymerizates of butadiene or 2-halobutadiene-1,3 or copolymers of 'such a com'pound with at least one other compound polyinerizable therewith which contains an olenic linkage.l Such other polymerizable compounds contain atleast one olenic linkage therein which enables the `coupling of `these molecules with the butadiene or haloprene molecule to form copolymers. Suitable copolymer elastomers of butadiene include lnterpolymerizates of butadiene with one or. more compounds such as chloroprene, bromoprene,

butadiene,i and the like. The polymers of haloprenes are polymerizates of such compounds as pentadiene, methyl pentadienes, and the like.

While the polymerizates may be those obtained with' the aid of sodium, boron trifiuoride, etc., as catalyst, it is preferred to have the elastomers of the' compositions prepared by emulsion polymerizates vusing organic peroxides, inorganic `pei-salts, etc., as catalyst.

'I'he proportion of the halogenated alkyl ethers can vary considerably in the compositions, depending to a. largeextent upon the particular substance contained therein and the use to which the composition is put. Ordinarily 5 to 40 parts of the ether per 100 parts of polymer by weight are suitable, although in special cases a greater or lesser proportion is employed. A preferred range is l0 to 30 parts of softener per 100 parts of polymer. In general, the larger the proportion of ether, the more tacky and plastic is the composition. Further, the larger the proportion of ether, the greater is the flexibility and elongation of the vulcanizate, but the lower is its tensile strength.

The halogenated alkyl ether softener is incorporated into the polymer by milling, preferably with a friction roll mill. The incorporation is eiected with mills maintained at lower temperatures than are ordinarily employed in milling or masticating natural rubber Temperatures not higher than about 50 C. are to be recommended for the rolls in preparing the comphenoprene, isoprene, isobutylene, styrene, di-

positions.

While the foregoing description has emphasized the ether softener and the rubber-like synthetic elastomer in the compositions, the presence of various other ingredients is necessary and desirable to be therein for enabling preparation of a vulcanizable composition. Thus. in preparing a composition for processing or vulcanizing to a finished rubber article, a number of substances are also incorporated into the composition.

In the case where a, polymer or copolymer of butadiene is used in the composition subjected to vulcanization treatment, anumber of ingredients are present in addition to the ether softener.' Incorporated in the composition is a vulcanizing agent such as sulfur or a sulfur liberating compound which is vital to eiecting vulcanization of the polymer. The composition may contain an anti-oxidant or age retarder amine, 2,2,4-trimethyl-1,2,dihydroquinoline, pnitrosodimethylamine, etc. On organic accelerator is included such as benzothiazyl disulfide, tetramethylthiuram disulde, dibutylxanthic disulde, mercaptobenzothiazole, benzothiazyl disulde, zinc salt of mercaptobenzothiazole, etc., together with an activator for the accelerator such as zinc oxide. An inorganic accelerator such as litharge can be used alone or in conjunction with one or more organic accelerators.' Various powdered materials may be ed alkyl ethers as softener Tests were madeA on the unvulcanized Acouipounds to determinecomparative tackiness and plasticity, the results of which are given'in the lauric acid and waxes, either paralnic or natural. The incorporation oi these various substances may be e'ected by milling. d

In a similar manner, a n r of ingredients are usefully incorporated with the compositions of elastomers of a-halop'rene. As vulcanizing agents, such compositions contain a metallic oxide such as magnesium oxide, zinc oxide or lead oxide which substances also function as stabilizing agents for the unvulcanizedcompositions. If f desired, the composition may contain sulfur as a substituent although it iunctions primarily as a vulcanization accelerator with haloprene elastomers. Organic vulcanization accelerators are sometimes useful while the incorporation of anti'- oxidants, a number of particular compounds of which were indicated above, impart age and heat resisting qualities to the vulcanizates. Various fillers used in compounding with butadiene polymerizates .may be used 'in compounding with haloprene polymers. Such substances as stearic acid, wood rosin, paraffin wax are also' of utility in the compositions. While the compositions contain the halogenatvarious other sof-- -teners may be incorporated in minor amounts such as process oils, coal tar softeners, mono or dicarboxylic acids and the like.

The compositions containing the various ingredients are useful as lcompounded rubber-like esters of 5 materials which may bla vulcanized. The vul- 1 canization of the compounded compositions is effected in the usual well-known manner by application of heat and pressure in a mould, while the optimum conditions of vulcanization will vary with the ingredients present in the compositions. Times of cure of from l0 minutes to one hour are suitable with press temperatures' of from 140 C. to 175 C. In this manner a great num- -her of useful rubber articles may be prepared from thepcompositions.

For the purpose of further' illustrating the-invention, the following` examples are given, it being understood that specic details given therein are not to be construed as limitative.

` Example I A synthetic rubber composition of the invention was compounded using a polymer i'rom`2- chlorobutadiene- 1,3 known under the trade-mark of Neoprene F. R. with the softener'tetrachloro dipropyl etherv (bis-(betmgamma propyl) ether) and another compound was prepared 'with dibutyl sebacate, als'oftener in commercial'use for comparative purposes. The compounded mixtures were prepared according to the formula below, the ingredients. having been added in the order following table, along with values obtained in the tests on the vulcanizates of portions of the two compounds which were subjected to differentV times of cure at 153 C.

Sofneriw parts t Tetraohloro partsneoprene IRQR.) dipropyl ether Dlbmyl *bmw Time of incorporation f m 4 3 Unvulcanized compound:

ack load 21 20 Plasticity load v 10.3 6.9 Vnlea izate:

Time ofcure V min. at 153 C.. Il 30 45 i!) 30 45 Tensile strength lbs./sq.i!1 1,408 1,100 1,404 1,336 1,256 1,12) Ultimate elongation 'percent. 285 283 281 292 276 246 Modulos at 300% elongation iba/min.. 1,480 1,480 1,480 1,410 1,390 1,460 -Durometer ha ess' 50 58 58 55 56 56 ,Abrasion cnc/horsepower hr.. 139 135 131 118 122 129 Rebound per cent offalL. 51.5 52.0 52.0 54.0 54.0 54.0 Stiifening temperl ature C -37 -40 In the above table, the values given for tack which was the temperature at which a bent sample of the vulcanizate fails to resume its original shape in ilve seconds.

The "fiat" character of the most importantI properties of the vulcanizate compositions containing tetrachloro dipropyl ether as compared with those of compositions containing dibutyl v sebacate is illustrated in the graphical representation shown in Figures 1, 2, 3 and 4 'of the accompanying drawing.

Figure 1 is -a plotcf tensile strength in lbs. per

sq. in. on the ordinate axis and time of cure in minutes on the abscissa axis for vulcanizates of the chloroprene polymer containing tetrachloro dipropyl ether or dibutyl sebacate as softener.

Figure 2 is a plot of the ultimate elongation in per cent at which the sample broke when stretched on the ordinate axisand time of cure in minutes `on the abscissa axis for the vulcanizates containing tetrachloro 'dipropyl ether or` dibutyl sebacate.

Figure 3 is a plot of modulus at 300% elongation in lbs. persq. Tin on' the ordinate axis, and time of cure in minutes on the abscissa axis i'or vulcanizates Vcontaining the two different softeners.

Figure 4 is a plot'of abrasion in cc. per horse- A powe hr. on ordinate axis, and time of cure in listed: 05

. H Part by Ingredient weight Neo rene F. R 100 Magxziasium oxid 4. 0 70 Softener (tetrach oro di ropyl ether or d utyl sebacate) l0. 0 Phenyl alpha-naphthy amine 2,0 Soit carbon b1ack-- 35.0 Channel black l5. 0 S ur- 1.0

Zinc oxide..- 5.0 's

minutes on the abscissa axis for vulcanizates of the polymer containing tetrachloro dipropyl ether or. dibutyl sebacate as softener.

The improvement in compositions containing tetrachloro dipropyl ether over -a conventional softener, dibutyl sebacate, is evident from the graphical representations which illustrate that 4 the compositions of the invention obviate the -criticalness of the time of cure and permit uniform properties to be obtained throughoutV a large article of 'manufacture even though the inner parts of that article are subjected to shorter times of curing temperature than the outer parts owing to the slowness of heat transfer from the Y outer parts to the inner parts in moulded vulcanizates of the compound. Further, the graphical representations show that even though the time of cure is varied, the compositions permit articles of substantially .uniformproperties to be obtained.

Example I! Synthetic rubber compositions were prepared from a copolymer of butadiene and acrylonitrila. known under the trade-mark Hycar O. R., using tetrachloro dipropyl ether (bis-(beta, gamma propyl) ether) or dibutyl phthalate, the latter being a known softener. The compositions were compounded according to the -following formula,

the constituents being added in the order listed 'Properties' of the two compounded mixtures were tested, both for the unvulcanized compound and the vulcanizate obtained after thirtymin'- utes cure at 153 C. which results are tabulated torrione-1,3, containing an oiefinio linkage, and polymerizates of butadiene-1,3 and another polymerlzable compound containing an olenic linkage, and, as softening agent therefor, a halogenated alkyl ether wherei-n each of the alkyl groups linked to the ethereal oxygen atom contain three to eight carbon atoms, to each of which are attached atleast two halogen atoms, but are devoid of any halogen atoms attached to" the alpha carbon atoms thereof.

2. A composition-of matter comprising a vulcanizate of the composition of claim 1.

3. A composition of matter vcontaining a copolymer of butadiene-1,3 with acrylonitrile and from 5 to 40 :parts by weight of a softener per 100 parts of said copolymer, said softener being tetrabelow:

Tetrachloro Softener (25 parts per 100 parts Dibutyl yon o. a.) digy phthalate Time of inco eration min.. 9 22 Unvuloanize compound:

Tack load 48 m Plasticity load Z). 4 10. 4 Vulcanizate:

Time of cure ;min. at 153 C.. Il) 30 Tensile strength..- 1bs./sq. in-. 3, 100i 2, 866v Ultimate elongation per cent.. 52) 560 Modulus at 300% elongation lbs/sq. in 1,380 1,070 Durometer hardness 60 63 Abrasion oa/horsepower hr A21 71 Rebound per cent of fall. .0 25 0 Stiffening temperature C -11 -14 The excellent properties ofthe composition of Athe invention as compared to that of the composition containing dibutyl phthalate are evident from the ltable to which is coupled the name-resistant qualityv owing to the presence of the 'tetrachloro dipropyl ether which is not obtained with the composition containing dibutyl phthalate, an inflammable substance.

' a -halobutadiene-l. polymerizates ofbutadiene 1,3, polymerizates 0I 2-ha10biltadlenef1 and qanother'polymerizabie compound, other'thanb'- chloro dipropyl ether, said ether being devoid of any' chlorine atoms attached to the alpha carbon atom thereof.

4. A composition of matter comprising a vulcanizate of the composition of claim 3.

5. A composition of matter containing a polymerizate of 2chlorobutadiene1,3 and from 5 to 40 parts of a softener per 100 'parts of said polymerizate, said softener being a chlorinated alkyl ether wherein each of the alkyl groups linked to the ethereal oxygen atom contain three to eight carbon atoms, to each of whichare attached at least two chlorine atoms, but are devoid of any chlorine atoms attached' to the alpha carbon atom thereof.

6. A composition of matter comprising a vulcanizate of the composition 0f claim 5.

7. A composition of matter containing a copolymer of 2-ch1orobutadiene1,3 and another polymerlzable compound having an olenic linkage and from 5 to 40 parts of a softener per 100 parts of said copolymer, said softener being a chlorinated alkyl ether wherein each of the alkyl groups linked to the lethereal oxygen atom contain three to eight carbon atoms, to each of which are attached at least two chlorine atoms, but are devoid of any chlorine Vatoms linked to .the alpha carbon atom thereof. Y

8. A composition of matter 'comprising a vulcanizate of the composition of claim 7.

9. A composition of matter` containing a copolymer of 2-chlorobutadiene-L3 and another polymerizable compound having an olefinic Imk- Vage and as a softening agent therefor, from 10 canizate of the composition of claim vil.

11. A composition of matter containing a vcopolymer of 2-chlorobutadiene-L3 and-another lpolymerizable compound having an olefinic linkage and as a softening agent therefor, from 10 to 30 part of tetrachloro diisobutyl ether, said4 ether being devoid of any .chlorinel atoms atl tached to the alpha Acarbon atom thereof.

f 12. A composition of matter comprising a vulcanizateof the composition of claim 11.

' 13. A composition of matter comprising a polymer Afromthe class consisting of .polymerizates of a. Z-'haIobutadiene-l, polymerizates of butadiene-1,3, polymerizates of 2-halobutadiene other polymerizable compound containing an oleflnici linkage, and, as agent therei aanname fore, the compound represented by the formula CHaCl-CHCl-CHn-O-CHz-CHCl-CHRCI 14. A composition of matter comprising a vulcanizate of the composition of claim 13.

15. A composition of matter containing a copolymer of 2-chiorobutadiene-L3 and another poiymerizable compound having an oietinic linklage, and, as a softening agent therefor, from 10 momma: w. EVANS. 

